- Electrophilic Hypervalent Trifluoromethylthio-Iodine(III) Reagent
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Herein we report the design and synthesis of hypervalent trifluoromethylthio-iodine(III) reagent 1 and the elucidation of its structure by NMR spectroscopy and X-ray crystallography. The trifluoromethylthiolation reactions of 1 with various nucleophiles were explored, and this compound was found to be a versatile electrophilic reagent for the transfer of a trifluoromethylthio group (-SCF3). The hydrogen-bonding mode responsible for the activation of 1 by the solvent 1,1,1,3,3,3-hexafluoro-2-propanol was investigated both experimentally and computationally.
- Yang, Xiao-Guang,Zhang, Chi,Zheng, Ke
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- Oxidative trifluoromethylselenolation of 1,3-dicarbonyls with [Me4N][SeCF3]
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Reactions of 1,3-ketoesters, -diesters, -diketones, and -ketoamides with [Me4N][SeCF3] in the presence of an appropriate oxidant provided a series of 2-trifluoromethylselenolated 1,3-dicarbonyls in moderate to good yields. The trifluoromethylselenolation featured simplicity, mildness, high efficiency, transition-metal-free conditions, and compatibility of various oxidants, and represented the first oxidative trifluoromethylselenolation of 1,3-dicarbonyl compounds with [Me4N][SeCF3]. This protocol was also applicable to the oxidative trifluoromethylthiolation of 1,3-dicarbonyls with [Me4N][SCF3]/NCS, and oxidative trifluoromethylchalcogenation with nucleophilic XCF3 (X = O, S, and Se) reagents were compared. The results demonstrated that these nucleophilic XCF3 salts showed different reaction profiles towards 1,3-dicarbonyls under oxidation conditions.
- Dong, Tao,Tan, Kai-Li,Zhang, Cheng-Pan,Zhang, Xue-Qiong
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supporting information
p. 1769 - 1779
(2020/03/17)
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- Preparation method of alpha-trifluoromethylthio substituted acetophenone compound
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The invention discloses a preparation method of an alpha-trifluoromethylthio substituted acetophenone compound. The preparation method comprises the following steps: by taking aryl ketone as a substrate, sodium trifluoromethanesulfinate as a trifluoromethylthio reagent, triphosgene as an additive, pyridine as a catalyst and dichloroethane as a solvent, in the nitrogen protection mode, stirring for12 hours at the temperature of 60 DEG C, performing a TLC tracking reaction, and conducting column chromatography isolation after sufficiently completing the reaction, thereby obtaining the alpha-trifluoromethylthio substituted acetophenone compound. According to the preparation method, the triphosgene is used as the reaction additive, so that using an expensive trifluoromethylthio reagent is avoided, but so far, a method for introducing trifluomethylthio has not been reported, the preparation method is simple and convenient, is low in cost, and is high in yield, a product is directly obtained, without any transition metal catalysis, and therefore, the preparation method is extremely high in practical popularization value.
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Paragraph 0065; 0067; 0068; 0069
(2018/10/19)
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- Exploration of the Synthetic Potential of Electrophilic Trifluoromethylthiolating and Difluoromethylthiolating Reagents
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The electrophilicity parameters (E) of some trifluoromethylthiolating and difluoromethylthiolating reagents were determined by following the kinetics of their reactions with a series of enamines and carbanions with known nucleophilicity parameters (N, sN), using the linear free-energy relationship log k2=sN(N+E). The electrophilic reactivities of these reagents cover a range of 17 orders of magnitude, with Shen and Lu's reagent 1 a being the most reactive and Billard's reagent 1 h being the least reactive electrophile. While the observed electrophilic reactivities (E) of the amido-derived trifluoromethylthiolating reagents correlate well with the calculated Gibbs energies for heterolytic cleavage of the X?SCF3 bonds (Tt+DA), the cumol-derived reagents 1 f and 1 g are more reactive than expected from the thermodynamics of the O?S cleavage. The E parameters of the tri/difluoromethylthiolating reagents derived in this work provide an ordering principle for their use in synthesis.
- Zhang, Jingjing,Yang, Jin-Dong,Zheng, Hanliang,Xue, Xiao-Song,Mayr, Herbert,Cheng, Jin-Pei
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p. 12690 - 12695
(2018/09/25)
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- Thio trifluoromethyl-containing compounds and methods for their preparation
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The invention discloses a compound containing trifluoromethylthio group and a preparation method thereof. The invention discloses a compound 7, compound 9 or compound 11 containing trifluoromethylthio group. The invention provides a preparation method of the compound 7, 9 or 11, which comprises the following steps: in an organic solvent, carrying out substitution reaction on a compound 1 and a beta-eleostearate compound 6 in the presence of an alkali to obtain the compound 7; in an organic solvent, carrying out substitution reaction on the compound 1 and an aldehyde or ketone compound 8 in the presence of a catalyst and an additive to obtain the compound 9; and under the gas protection, carrying out substitution reaction on the compound 1, cuprous iodide and an alkyne compound 10 in an organic solvent in the presence of an alkali to obtain the compound 11. The preparation method of the compound 7, 9 or 11containing trifluoromethylthio group has the advantages of mild reaction conditions, high conversion rate, high yield and low production cost, and is suitable for industrial production.
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Paragraph 0175; 0176; 0177; 0178
(2016/10/17)
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- Acid-Catalyzed Synthesis of α-Trifluoromethylthiolated Carbonyl Compounds
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The α-trifluoromethylthiolation of carbonyl compounds in soft acidic conditions has been developed. With this method only mono-trifluoromethylthiolation was selectively observed. Base-sensitive ketones can then be trifluoromethylthiolated. More sensitive
- Alazet, Sébastien,Ismalaj, Ermal,Glenadel, Quentin,Le Bars, Didier,Billard, Thierry
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p. 4607 - 4610
(2015/08/03)
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- Structure-reactivity relationship of trifluoromethanesulfenates: Discovery of an electrophilic trifluoromethylthiolating reagent
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A family of electrophilic trifluoromethanesulfenates was prepared. Structure-reactivity relationship studies showed that the substituted groups on the aryl ring of the trifluoromethylthiolating reagent did not have an obvious influence on their reactivities. A simplified electrophilic trifluoromethylthiolating reagent 1c was then identified that can react with a wide range of nucleophiles such as Grignard reagents, arylboronic acids, alkynes, indoles, β-ketoesters, oxindoles, and sodium sulfinates under mild reaction conditions. A variety of functional groups were tolerated under these conditions.
- Shao, Xinxin,Xu, Chunfa,Lu, Long,Shen, Qilong
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p. 3012 - 3021
(2015/03/30)
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- N-trifluoromethylthiosaccharin: An easily accessible, shelf-stable, broadly applicable trifluoromethylthiolating reagent
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A new, electrophilic trifluoromethylthiolating reagent, N-trifluoromethylthiosaccharin, was developed and can be synthesized in two steps from saccharin within 30minutes. N-trifluoromethylthiosaccharin is a powerful trifluoromethylthiolating reagent and allows the trifluoromethylthiolation of a variety of nucleophiles such as alcohols, amines, thiols, electron-rich arenes, aldehydes, ketones, acyclic β-ketoesters, and alkynes under mild reaction conditions. 'Sacch'ed out: A new, electrophilic trifluoromethylthiolating reagent, N-trifluoromethylthiosaccharin (1) can be synthesized in two steps from saccharin within 30minutes. The reagent 1 allows the trifluoromethylthiolation of a variety of nucleophiles such as alcohols, amines, thiols, electron-rich arenes, aldehydes, ketones, acyclic β-ketoesters, and alkynes under mild reaction conditions.
- Xu, Chunfa,Ma, Bingqing,Shen, Qilong
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supporting information
p. 9316 - 9320,5
(2014/10/15)
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- Trifluoromethanesulfonyl hypervalent iodonium ylide for copper-catalyzed trifluoromethylthiolation of enamines, indoles, and β-keto esters
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A novel electrophilic-type trifluoromethylthiolation reagent, a trifluoromethanesulfonyl hypervalent iodonium ylide, was designed and reacted well with various nucleophiles to afford the desired CF3S-substituted products. In situ reduction of t
- Yang, Yu-Dong,Azuma, Ayaka,Tokunaga, Etsuko,Yamasaki, Mikio,Shiro, Motoo,Shibata, Norio
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supporting information
p. 8782 - 8785
(2013/07/26)
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- THE REACTION OF β-DICARBONYL COMPOUNDS WITH TRIFLUOROMETHYL-SULPHENYL CHLORIDE. PART I. CF3S-SUBSTITUTED ESTERS, ANILIDES OF β-KETO ACIDS, AND THEIR SCHIFF BASES: SYNTHESIS AND STABILITY
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The reactions of the β-keto acid derivatives with trifluoromethylsulphenyl chloride were carried out to give the α-SCF3 substituted esters, anilides and their Schiff bases of acetyl- and benzoylacetic acids.Ethyl esters of α-(trifluoromethylthio)acetoacet
- Kosala, A.
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